Process for the dyeing of fibrous materials



Patented Sept. 2, 1941 Walter Kling, Ernst Goette, Kurt Heide, and Herbert Gerstner, Chemnitz, Germany, assignors, by mesne assignments, to .Patcheni Aktiengesellsohait Iur Beteiligung an Patenten und sonstigen Erfindungsrechtcn aui' chemische Verfahren, Zurich, Switzerland, a Swiss corporation No Drawing. Application September 18, 1934, fggigalllo. 744,606. In Germany September 22,

This invention relates to the dyeing of fibrous materials and has for its principal object improvements in dyeing processes of varied character, and in the baths which are employed in dyeing. whereby such processes may be facilitated and greater uniformity and deepening of the color in the finished product may be secured.

It is one of the features of the invention that the field of use of. conventional deystufi's is ma-. terially extended. For instance, in the dyeing industry it has hitherto been accepted as an axiom that certaindyestufis may be satisfactorily used only for vegetable fibers, others essentially only for animal fibers. It is now discovered-that with the aid of compounds which are capable of giving 03 surface active cations in dyeing and printing, the power of attraction or afllnity of the direct dyes and acid dyes can be so afiected that pure cotton dyestuifs canbe employed for the dyeing of woolen materials or, alternatively, pure wool dyes can be brought to a state of complete absorption on cotton fibers or artificial silk. Furthermore, by suitable use in the dye bath of .these compounds, 9. material deepening of the dy colors is obtained regardless of the nature of the fiber.

pounds derived from aliphatic tertiary amines, for example triethyl cetyl ammonium iodide or bromide.

In lieu of the quaternary ammonium compounds, the analogous high molecular phosphonium or sulphonium compounds may be used, for instance decyl phosphonium iodide, dodecyl phosphonium bromide, tetradecyl phosphonium the quaternary ammonium compound prepared by the addition of the dodecyl ether of a-glycerine Among the more important compounds which I yield surface active cations are the high molecular. quaternary ammonium compounds, ammonium salts containing high molecular aliphatic residues, and in particular the compounds derived from heterocyclic nitrogen bases, such as the pyridine bases, these be-v compounds, further substitution products'of alithesecompounds, aswell as the corresponding halides. Analogous derivatives of other hetero-. cyclic nitrogen bases such as quinoline and isoquinoline may also be employed.

Less readily accessible but similarly useful are the quaternary ammonium compounds derived from diamines and containing higher alkyl or aliphatic acid residues as well as similar combromhydrine C11H2aCI-Iz.O.CHzCHOH.CH2Br to pyridin, the quaternary ammonium compound formed by'the addition of bromine-acetic acid dodecyl ester BrCHz.COO.CI-Iz.CuHn to chinoline. The following examples of speciflccompounds indicate generally the nature of the formulae so far as they are known:

' Decyl phosphonium iodide C "Kn alkyl alkyl alkyl Dodecyl sulphonium iodide 0 min alkyl+l Tetradecyl pyridinium sulphate can, \OSOIE Octadecenyl chinolininm iodide Heptyl isourea bromide [H;N.O (0.C1H10):NH]Br I Decyl isothiourea iodide [H;N.C(S.C||Ha) lI Addition product of tetradecyl bromide to hexamethylenetetramine Heptyl guanidine HaN N.C1H1| HaN ' dditi n roduct of glycerine bromhydrine dodecyl ether A o p to pyridine Br cntcnomcmocmcun Addition product of bromine-acetic acid dodecyl ester of chinoline These compounds may be added either directly to the dye bath or employed for-preliminary treatment of the material to be dyed. Thus an extraordinary deepening of the dye color may for example a fatty alcohol sulphate or sulphonate. The coloring of the fabric is still further improved if, after the preliminary treatment with dodecyl pyridinium sulphate or an analogous compound, the material is dyed in a dye bath to which has been added a mixture oi both types of compound hereinbefore referred to, for instance one part sodium salt of the technical dodecyl sulphuric acid ester and three parts of dodecyl. pyridinium sulphate.

In lieu of the fatty alcohol sulphuric acid esters and their salts, which are preferred for the purposes herein indicated as surface active anion yielding compounds, various substitutes may be employed, such as all high molecular aliphatic or cycloaliphatic sulphuric acid esters or true sulphonic acid as well as corresponding phosphoric acid esters. The alkali salts of sulphuric acid esters of the low boiling portions of the alcohols corresponding to the fatty acids of coconut oil, obtainable from the latter by reduction, are par;- ticularly satisfactory. Such alcohol mixtures contain principally the alcohols of 6 to 12 carbon atoms. 4

As applied to the dyeing of animal fibers with acid dyes, the use of quaternary ammonium salts promotes the absorption of the dyes at lower temperatures, for instance 40 C. which is important when sensitive materials are to be dyed.

It is also feasible, however, to bring a'cid dyes to absorption on plant fibers such as cotton or artificial silk, if such fibers are given a preliminary treatment with dodecyl pyridinium sulphate or the like and then dyed either in the normal manner or with the addition to the dye bath of a mixture of dodecyl pyridinium sulphate and fatty alcohol sulphate in which the former predominates.

This process is particularly important in the dyeing of part wool material, since the same dyestuif can be employed to obtain uniform coloring of both types of fiber present in the mixed woven goods; Thus mixed goods of animal and plant fiber can be treated, for instance, with a mixture of wool dye and direct dye after a preliminary treatment of the mixed goods with dodecyl pyridinium sulphate or the like, thereby causing both dyes to be absorbed uniformly by both kinds of fiber.

As an example, by means of Sirius orange C and alizarin blue (pure) B (German Patent 126,392) with admixture of 20% common salt, a greenish coloring of both kinds of fiber of the mixed goods with 2% Sirius orange G (Schultz, Dye Tables,

7th edition, volume 2, page 198) with the simultaneous employment of 20% sodium chloride in the absence of acid, only a soiling of the fiber occurs, and this can be almost completely removed by washing. On the other hand, if the wool is treated before dyeing with a compound such as hereinbefore described, for instance dodecyl pyridinium sulphate, strong and fast colors can be produced by the subsequent dyeing operation, the operation being facilitated, if

necessary, by the further addition of a less quan-' may be secured, whereas without the preliminary treatment the animal fiber would be colored blue and the plant fiber yellow.

The promotion of the absorption of direct dyes by animal fibers is a matter of great importance and may be facilitated by adding to the dye bath a quaternary ammonium compound or the like. The use of such compounds in the silk dyeing industry is also of importance, particularly in dyeing at lower temperatures, such temperatures being frequently necessary in the batik'industry because of the low melting point of the waxy masses serving as a reserve.

It is further possible, by a preliminary treatment of acetate silk with dodecyl pyridinium sulphate or similar compounds, to cause direct dye stuffs to adhere to the fibers, such adherence being possible heretofore only through surface saponification of the cellulose acetate. In dyeing with the acid dyes heretofore used for acetate silk, commonly referred to as cellite fast dyes, the preliminary treatment with surface active quaing superfluous the numerous precautionary,

measures heretofore adopted for the purpose of obtaining uniform dyein considerable simpliflcation of the dyeing procedure resulting. Thus in the case of dyeing with basic dye stufis on premordanted goods, it has heretofore been neces-. sary to ensure that the mordant should be used in the proper ratio to the strength of the dyestufl, goods too strongly premordanted absorbing the dye too rapidly and consequently promoting uneven dyeing. It was also considered necessary to add the dyestuii' in portions to the bath and to begin dyeing in the cold, gradually increasing the temperature. All of these precautionary measures have been found unnecessary, if substances giving off surface active cations such as hereinbefore enumerated are employed.

For example, if we dye artificial silk premordanted with.6% catanol N (Schultz, Dye Tables, 7th edition, volume 2, page 303) at 70 C. with 0.5 grammalachite green (German Patent 4,332) and fail to employ the special agent defined herein, the dyeing will be wholly uneven. 0n the contrary, if one gram per liter of dodecyl pyridinium sulphate is added to the dye bath,

the dyeing will be quite uniform and so strongly' retained that the bath is not extracted and the coloring is correspondingly light. If a smaller quantity of this special agent is employed, or if a second agent giving ofi surface active anions is subsequently added, for instance the alkali salt of a fatty alcohol sulphuric acid ester, a

complete extraction of the dye bath can be effected and a very even coloring obtained.

By suitable treatment of the bath with the proper proportions of the surface active cation and anion yielding substances, which to the extent indicated above oppose each other, the dyeing process may be very accurately controlled and any desired degree or speed of extraction can be obtained, so that the dyeing may be carried out wholly independently of conditions heretofore considered absolutely necessary.

It has also been found that the depth of the color dyed as well as the dyeing throughout of thick materials in the employment of vat dyes can be effectively promoted in accordance with the slop padding process if the fibrous materials are treated with substances giving off surface active cations prior to the slop padding of the dye stuff. As heretofore indicated, such substances as the'quatemary higher molecular ammonium compounds and particularly those derived from heterocyclic nitrogen bases, such as pyridine for example, are of special importance in this connection since they are more readily accessible.

Example I Artificial silk is given a preliminary treatment with a solution of three grams per liter of dodecyl pyridinium sulphate in the dye bath pro portion of 1:20 at 70 c centrifuged ed, and then slop padded with 1 gram per liter indanthrene blue-green, B powder (Schultz, Dye Tables, 7th edition, volume 2, page 127) with a dye bath ratio of 1:20 and a temperature of 50 C. After wenty minutes it is wound off as uniform- 1y as possible and developed in a fresh bath containing 20 cm. per liter sodium hydroxide 32 B. and 5 grams per liter of hydrosulphite at 50 to 60v C. An intense green color is obtained, whereas without such 'preliminarytreat ment 9. materially less intense coloration results.

In the making of aniline black dyes and other oxidation dyes it has been previously the cuetom to employ boiled and bleached fibrous materlals, since it was believed that uniform precipitation of the dye could not be obtained on unsized, unbleached raw materials. It is now found that oxidation dyes can be printed or dyed with excellent results on unsized, unbleached raw materials, provided substances capable of giving 7 off. surface active cations are added to the dye baths. For instance to a dye bath containing aniline salt or salts of other suitable aromatic bases such as p-phenylene diamine, or n-amino phenol, special agents of the character hereinbefore described, and particularly quaternary ammonium salts with high molecular aliphatic residues, can be added.

In addition to the excellent wetting and equalizing action of such agents, the fibers are saved and the resistance to tearing exhibited by, the

goods before treatment is much less adversely aflected than if such agents are not employed. These advantages are also derived in some degree by the use of such agents in dyeing and printing on preliminarily bleached materials, although the equalizing action is particularly striking when comparison is made of the action of the dyes on unfinished goods produced with and without the addition of the quaternary ammonium salt or the like.

Example II Piece goods which have not been prewetted or boiled are impregnated on a suitable dye Spreading machine with a solution of Grams Aniline chlorhydrate 100 Aniline 44': Sodium sulphite 2 Potassium ferrocyanide 84 Sodium chlorate 38 Decyl pyridinlum sulphate 2-4 per 1.2 liters of the bath The goods arethen dried, briefly steamed,

treated with chromate, washed, and dried. An

excellent dye color and a deep even black results. Before the steaming or before the impregnation a suitable reserve can' be impressed by known methods for the production of terned goods.

, The-various other agents hereinbefore indicated can be substituted for the dodecyl pyridinium sulphate employed in the preceding ex- Y ethyl ethylene diamine, as well as corresponding phosphonium and sulphonium compounds with high molecular substituents,;may be used.

"'or printed condition in the usual way.

Example HI In a single bath which contains Grams Aniline sa 100 p-Phenylenediamine 4-8 Ammonium sulphite 3 Sodium chlorate 30 Copper sulphate 3 Dodecyl pyridinium sulphate 2-4 per 1 liter of bath cotton yarn, not prewetted or boiled, is dyed green, oxidized and washed. The black yarn obtained is very uniform, deep black, proof against rubbing off, does not turn green, and exhibits an excellent degree of fastness.

per 1 liter of bath is slop padded on a suitable machine on a nonbleached goods, dried, and finished in unprinted The resultant product is a uniform, brown colored or uniformly patterned goods.

In vat dyeing it' has heretofore been customary, in order to secure uniformity. to add to the vats ricinoleic' soaps sulphonated oils, Turkey red -oil soap, and similar agents. Subsequently, in

order to secure in such a process a stronger adherence of the dye, still more dye must be added to the dye bath, since the known leveling means retains a portion of the dye in the bath and prevents its absorption. It is found that by the employment of two different types of surface.

equivalent to reserve action. By then adding wetting agents which form surface active anions, for example by adding suitable amounts of the fatty alcohol, sulphates or sulphonates hereinbefore described, the dye retaining action can be advanced or retarded at will. By this process any degree of absorption of the dye originally retained can be secured by properly balancing the action of the two'special ingredients; under some conditions complete extraction from; the bath can be secured. Since the admixture can be gradually effected, the capillarity of the. dye

canbe made stronger the longer the dyeing is continued.

If desired the process may be carried out by: the initial addition of a quaternary, high. molecphuric acid ester, more dyestufl introduced and dyeing continued. .It is frequently advantageous to try a parent solution of the quaternary ammonium salt in order to weaken the powerful action and to carry out the proper treatment of the bath. The fatty alcohol sulphate or the like can also be prepared in-the form of a parent solution, but this is ordinarily not necessary.

In addition to effective leveling action obtained by this process, there is a marked improvement in the dyeing through the entire depth of very tightly woven goods and highly twisted yarns. i The vats last, stay clear, show avery slight bloom,

foam, and exhibit at the same time intensive wetting action. The process is particularly advantageous when applied to operations which are generallycarried out on machines but which required dyeing in the vat when difiicultly leveled dyes were employed owing to the slow movement of the machines.

Example V In-the dyeing of indanthrene blue-green FFB powder (Schultz, Dye Tables, 7th edition, volume Example IV A solution consisting of i Grams p-Phenylenediamine 15-20 Sodium sulphoiwlate 1-1.5'-

Sodium chlorate; 15-20 Ammonium chloride 15-20 Tartar emet 1 Hexadecyl pyridinium chloride 2- 5 Ammonium vanadate solution l:1000 20 2, page 127) in bright color on bleached, mercerized, cotton yarn, where the main requirement is uniformity, the following vat dye may be used following vat dye is added:

ular ammonium salt or the like to a strongly stripping vat bath, a surface active anion yielding substance being thereafter added, for instance the sodium salt of a fatty alcohol sulfor the dyeing of 50 kgs. of goods:

Water 60 C -liters Soda solution 34 B ..do 15 Hydrosulphite conc. P.- kilograms 2 A 40% aqueous solution of lauryl pyridinium sulphate cubic centimeters" 500 Dyestufi in powder form, reduced in the main viat grams 250 The goods are introduced, soaked for twenty minutes, and then stretched out.

500 com. of a 30% aqueous solution of sodium salts of fatty alcohol sulphuric acid esters from the low boiling fractions of the alcohols obtained by reduction of the fatty acids, are then added and dyeing is continued. In order to-obtain the standard product, grams of dyestufi are added, reduced in the vat, and complete dyeing follows.

After the addition of the fatty alcohol sui-.

phate, a strong leveling action is invariably observed, which in the present instance is maintained for the purpose of securing better dyeing all the way through, the action being undiminished by further addition of larger quantities of fatty alcohol sulphate. The somewhat higher consumption of dyestuflf is an immaterial factor' in the total cost.

Example VI Unbleached mercerized cotton yarn is dyed a medium dark color by indanthrene brilliant violet 4 R powder (Schultz, Dye Tables, 7th edition, volume 2, page 1 28), the goods being treated in four portions of 50 kgs. each.

To the first portion, which is prewetted, the

Water 60 C l liters 1000 Soda solution 34 B do 15 Hydrosulphite cone. powder kilograms Indanthrene brilliant violet 4 R powder reduced in the main'vat grams 500 Lauryl pyridinium sulphate solution as in Example V "cubic centimeters-.. 500

The goods are introduced, soaked for ten minutes, and then stretched out. 1000 ccm. fatty alcohol sulphate solution as in Example V is claimed as new added, and the dyeing resumed for thirty minsmaller quantity of. a higher fatty alcohol sulutes more. The bath can then be diluted further phate; 1 by additional quantities of fatty alcohol sul- 3. A'process for improving the action of basic tinned and completed.

in the same manner as the second portion.

other vats,

Having thus described the and desired invention, what is to be secured by Letters Patent is:

. A process 4. A process for improving the dyeing and printing ofunsized. unbleached fibrous material with oxidation dyes, which comprises introducing in the dye bath a substance yielding surface active cations.

5. A process of dyeing animal and vegetable fibers-in approximately the same hetero atom and an alkyl radical of at least ten carbon atoms.

WAL'I'ER KLING ERNST GOE'ITE.

KURT HIDE 

